Anthranilamides, process for the production thereof, and pest controllers containing the same

ABSTRACT

To provide a novel anthranilamide compound or its salt which is useful as a pesticide; a process for its production; and a pesticide containing such a compound as an active ingredient. 
     An anthranilamide compound represented by the formula (I) or its salt. In the formula, R 1  is halogen, alkyl, haloalkyl, etc.; each of R 2  and R 3  which are independent of each other, is halogen, alkyl, haloalkyl, etc.; A is alkyl substituted by Y; Y is C 3-4  cycloalkyl which may be substituted by at least one substituent selected from the group consisting of halogen, alkyl and haloalkyl; m is from 0 to 4; n is 0 or 1; and q is from 0 to 4.

TECHNICAL FIELD

Patent Documents 1, 2, 3 and 4, respectively, disclose anthranilamidecompounds having certain specific chemical structures. However, nowherein such Patent Documents discloses compounds having alkyl substituted byC₃₋₄ cycloalkyl as a substituent corresponding to A in theafter-mentioned formula (I) of the present invention.

Further, Patent Document 5 discloses anthranilamide compounds having acyano group at the 4-position of the benzene ring. However, a cyanogroup is not contained in the definition of R¹ in the after-mentionedformula (I) of the present invention, and the respective chemicalstructures are different.

Patent Document 1: International Publication WO03/24222

Patent Document 2: International Publication WO03/15518

Patent Document 3: International Publication WO03/15519

Patent Document 4: International Publication WO01/70671

Patent Document 5: International Publication WO04/67528

DISCLOSURE OF THE INVENTION

Problems to be Solved by the Invention

For many years, many pesticides have been used, but many of them havevarious problems such that the effects are inadequate, their use isrestricted as pests have acquired resistance, etc. Accordingly, it isdesired to develop a novel pesticide substantially free from suchproblems, for example, a pesticide capable of controlling various pestswhich create problems in agricultural and horticultural fields or apesticide which is capable of controlling pests parasitic on animals.

Means to Solve the Problems

The present inventors have conducted various studies on anthranilamidecompounds in an effort to find a superior pesticide. As a result, theyhave found that a novel anthranilamide compound or its salt has anextremely high pesticidal effect against pests at a low dose and haveaccomplished the present invention. Namely, the present inventionrelates to an anthranilamide compound represented by the formula (I) orits salt:

wherein R¹ is halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl,haloalkynyl, alkoxy, haloalkoxy, alkylcarbonyl, haloalkylcarbonyl,alkoxycarbonyl, haloalkoxycarbonyl, phenoxycarbonyl which may besubstituted, nitro or formyl; each of R² and R³ which are independent ofeach other, is halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano; Ais alkyl substituted by Y; Y is C₃₋₄ cycloalkyl which may be substitutedby at least one substituent selected from the group consisting ofhalogen, alkyl and haloalkyl; m is from 0 to 4; n is 0 or 1; and q isfrom 0 to 4; provided that when R¹ is a fluorine atom, a chlorine atom,a bromine atom or methyl substituted at the 2-position of the benzenering and another R¹ is halogen substituted at the 4-position of thebenzene ring, the halogen at the 4-position is a fluorine atom or achlorine atom; a process for its production; and a pesticide containingit.

EFFECTS OF THE INVENTION

The pesticide containing, as an active ingredient, the novelanthranilamide compound represented by the above formula (I), has a veryhigh pesticidal effect against pests at a low dose.

BEST MODE FOR CARRYING OUT THE INVENTION

The substituents for the phenoxycarbonyl which may be substituted, inR¹, may, for example, be halogen, alkyl, haloalkyl, alkoxy, haloalkoxy,alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl,alkylsulfonyl, haloalkylsulfonyl, cyano and nitro. The number of suchsubstituents may be 1 or more, and if more, the respective substituentsmay be the same or different. Further, the positions for substitutionfor the respective substituents may be any positions.

The number of substituents Y in A may be 1 or more, and if more, therespective substituents Y may be the same or different. Further, thepositions for substitution of the substituents Y may be any positions.The number of substituents Y in A is preferably 1.

The number of halogen, alkyl or haloalkyl as the substituent for theC₃₋₄ cycloalkyl in Y, may be 1 or more, and if more, the respectivesubstituents may be the same or different. Further, the positions forsubstitution for the respective substituents may be any positions. TheC₃₋₄ cycloalkyl in Y is preferably unsubstituted, or when it has theabove substituents, the number of such substituents is preferably from 1to 5.

As the halogen or halogen as the substituent in R¹, R², R³ or Y, an atomof fluorine, chlorine, bromine or iodine may be mentioned. The number ofhalogens as substituents may be 1 or more, and if more, the respectivehalogens may be the same or different. Further, the positions forsubstitution of such halogens may be any positions.

The alkyl or alkyl moiety in R¹, R², R³, A or Y may be linear orbranched. As its specific example, C₁₋₆ alkyl such as methyl, ethyl,propyl, isopropyl, butyl, tert-butyl, pentyl or hexyl may be mentioned.

The alkenyl or alkenyl moiety in R¹ may be linear or branched. As itsspecific example, C₂₋₆ alkenyl such as vinyl, 1-propenyl, allyl,isopropenyl, 1-butenyl, 1,3-butadienyl or 1-hexenyl may be mentioned.

The alkynyl or alkynyl moiety in R¹ may be linear or branched. As itsspecific example, C₂₋₆ alkynyl such as ethynyl, 2-butynyl, 2-pentynyl or3-hexynyl may be mentioned.

As a specific example of the C₃₋₄ cycloalkyl or cycloalkyl moiety in Y,cyclopropyl or cyclobutyl may be mentioned, and cyclopropyl isparticularly preferred.

The salt of the anthranilamide compound of the above formula (I)includes all kinds so long as they are agriculturally acceptable. Forexample, an alkali metal salt such as a sodium salt or a potassium salt;an alkaline earth metal salt such as a magnesium salt or a calcium salt;an ammonium salt such as a dimethylammonium salt or a triethylammoniumsalt; an inorganic acid salt such as a hydrochloride, a perchlorate, asulfate or a nitrate; or an organic acid salt such as an acetate or amethanesulfonate, may be mentioned.

The anthranilamide compound of the formula (I) may have optical isomersor geometrical isomers, and such isomers and mixtures thereof are bothincluded in the present invention. Further, in the present invention,various isomers other than those mentioned above, may be included withinthe scope of the common knowledge in this technical field. Further;depending upon the type of such an isomer, the chemical structure may bedifferent from the above-mentioned formula (I), but it is obvious to oneskilled in the art that such a structure is in isomeric relation andthus falls within the scope of the present invention.

The anthranilamide compound of the above formula (I) or its salt(hereinafter referred to simply of the compound of the presentinvention) can be produced by the following reactions (A) and (B) and inaccordance with a usual method for producing a salt.

R¹, R², R³, A, m, n and q are as defined above, and Z is a chlorineatom, —OH or C₁₋₄ alkoxy.

In a case where Z is a chlorine atom, the reaction (A) can be carriedout usually in the presence of a base.

As the base, one or more types may suitably be selected for use from,for example, an alkali metal hydroxide such as sodium hydroxide orpotassium hydroxide; an alkali metal carbonate such as sodium carbonateor potassium carbonate; an alkali metal hydride such as sodium hydrideor potassium hydride; and a tertiary amine such as trimethylamine,triethylamine, triisopropylamine, diisopropylethylamine, pyridine,4-dimethylaminopyridine, 2,6-dimethylpyridine, 4-pyrrolidinopyridine,N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline,N-ethyl-N-methylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene or1,4-diazabicyclo [2.2.2]octane. The base may be used in an amount offrom 1 to 5 times by mol, preferably from 1 to 2.5 times by mol, to thecompound of the formula (II).

In a case where Z is a chlorine atom, the reaction (A) can be carriedout in the presence of a solvent, as the case requires. The solvent maybe any solvent so long as it is a solvent inert to the reaction. Forexample, one or more types may suitably be selected for use from, forexample, an ether such as diethyl ether, butyl ethyl ether,tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbonsuch as chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane, trichloroethane ordichloroethylene; an aromatic hydrocarbon such as benzene, toluene orxylene; a dipolar aprotic solvent such as acetonitrile, propionitrile,N,N-dimethylformamide, dimethylsufoxide, hexamethylphosphoric triamide,sulfolane, dimethylacetamide or N-methylpyrrolidone; an ester such asmethyl acetate, ethyl acetate or propyl acetate; and a ketone such asacetone, diethyl ketone, methyl ethyl ketone or methyl isobutyl ketone.

In a case where Z is a chlorine atom, the reaction (A) can be carriedout usually from −20 to +60° C., preferably from 0 to 30° C. Thereaction time is usually from about 1 to 24 hours, preferably from about2 to 12 hours.

In a case where Z is —OH, the reaction (A) can be carried out usually inthe presence of a dehydration condensing agent and a solvent.

The dehydration condensing agent may, for example, be a carbodiimidesuch as N,N′-dicyclohexylcarbodiimide, 1,3-diisopropylcarbodiimide or1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride; or otherssuch as 1,1′-carbonyl-bis-1H-imidazole, phenyl dichlorophosphate,diethyl phosphorocyanidate,1,3,5-triaza-2,4,6-triphosphorin-2,2,4,4,6,6-hexachloride, cyanuricchloride, isobutyl chloroformate, chlorosulfonyl isocyanate, ortrifluoroacetic anhydride.

The solvent may be any solvent so long as it is inert to the reaction.For example, one or more types may suitably be selected for use from,for example, an ether such as diethyl ether, butyl ethyl ether,tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbonsuch as chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane, trichloroethane ordichloroethylene; an aromatic hydrocarbon such as benzene, toluene orxylene; a dipolar aprotic solvent such as acetonitrile, propionitrile,N,N-dimethylformamide, dimethylsufoxide, hexamethylphosphoric triamide,sulfolane, dimethylacetamide or N-methylpyrrolidone; an ester such asmethyl acetate, ethyl acetate or propyl acetate; a ketone such asacetone, diethyl ketone, methyl ethyl ketone or methyl isobutyl ketone;and a aliphatic hydrocarbon such as pentane, hexane, heptane, octane orcyclohexane.

In a case where Z is —OH, the reaction (A) can be carried out usuallyfrom −20 to +60° C., preferably from 0 to 30° C. The reaction time isusually from about 0.5 to 24 hours, preferably from about 1 to 12 hours.

In a case where Z is C₁₋₄ alkoxy, the reaction (A) can be carried outusually in the presence of a base and a solvent. As the base, one ormore types may suitably be selected for use from, for example, an alkalimetal hydride such as sodium hydride or potassium hydride; an alkalimetal alkoxide such as sodium methoxide, sodium ethoxide or potassiumtertiary butoxide; and a tertiary amine such as trimethylamine,triethylamine, triisopropylamine, diisopropylethylamine, pyridine,4-dimethylaminopyridine, 2,6-dimethylpyridine, 4-pyrrolidinopyridine,N-methyl morpholine, N,N-dimethylaniline, N,N-diethylaniline,N-ethyl-N-methylaniline, 1,8-diazabicyclo[5.4.0]-7-undecene or1,4-diazabicyclo[2.2.2]octane. The base may be used in an amount of from1 to 5 times by mol, preferably from 1 to 2.5 times by mol, to thecompound of the formula (II).

The solvent may be any solvent so long as it is inert to the reaction.For example, one or more types may suitably be selected for use from,for example, an ether such as diethyl ether, butyl ethyl ether,tetrahydrofuran, dioxane or dimethoxyethane; an aromatic hydrocarbonsuch as benzene, toluene or xylene; a dipolar aprotic solvent such asacetonitrile, propionitrile, N,N-dimethylformamide, dimethylsufoxide,hexamethylphosphoric triamide, sulfolane, dimethylacetamide orN-methylpyrrolidone and an alcohol such as methanol, ethanol, propanol,n-butanol or tert-butanol.

In a case where Z is C₁₋₄ alkoxy, the reaction (A) can be carried outusually from 0 to 120° C., preferably from 20 to 80° C. The reactiontime is usually from about 0.5 to 24 hours, preferably from about 1 to12 hours.

The compound of the above formula (II) or (III) may be a known compoundor may be produced in accordance with known reference materials. Forexample, the compound of the formula (II) can be produced by or inaccordance with the method disclosed in Synthesis, 1980, p. 505. Thecompound of the formula (III) can be produced by or in accordance withthe method disclosed in schemes 9 to 22 in WO03/24222.

R¹, R², R³, A, m, n and q are as defined above.

The reaction (B) can be carried out usually in the presence of asolvent.

The solvent may be any solvent so long as it is inert to the reaction.For example, one or more types may suitably be selected for use from,for example, an ether such as diethyl ether, butyl ethyl ether,tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbonsuch as chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane, trichloroethane ordichloroethylene; an aromatic hydrocarbon such as benzene, toluene orxylene; and a dipolar aprotic solvent such as acetonitrile,propionitrile, N,N-dimethylformamide, dimethylsufoxide,hexamethylphosphoric triamide, sulfolane, dimethylacetamide orN-methylpyrrolidone.

The reaction (B) can be carried out usually from 0 to 120° C.,preferably from 20 to 80° C. The reaction time is usually about from 0.5to 24 hours, preferably from about 1 to 12 hours.

The compound of the above formula (IV) may be a known compound or may beproduced in accordance with a known reference material. For example, thecompound of the formula (IV) can be produced by or in accordance withthe method disclosed in Org. Prep. Proceed. Int., 1993, vol. 25, p. 585or the method disclosed in schemes 8 to 10 in WO03/24222.

The compound of the above formula (V) includes a novel compound. Such acompound can be produced by the Gabriel method, and can be produced, forexample, in accordance with the following reaction (C).

In the reaction (C), A is as defined above, and T is halogen, —OSO₂G (Gis a sulfonate residue) or —OH. When T is halogen or —OSO₂G, M is sodiumor potassium, and when T is —OH, M is a hydrogen atom. The abovesulfonate residue may, for example, be a C₁₋₆ alkyl such as methyl orethyl; or phenyl which may be substituted by C₁₋₆ alkyl.

In a case where T is halogen or —OSO₂G and M is sodium or potassium, thefirst step of the reaction (C) can be carried out usually in thepresence of a solvent.

The solvent may be any solvent so long as it is inert to the reaction.For example, one or more types may suitably be selected for use from,for example, an ether such as diethyl ether, butyl ethyl ether,tetrahydrofuran, dioxane or dimethoxyethane; an aromatic hydrocarbonsuch as benzene, toluene or xylene; a dipolar aprotic solvent such asacetonitrile, propionitrile, N,N-dimethylformamide, dimethylsufoxide,hexamethylphosphoric triamide, sulfolane, dimethylacetamide orN-methylpyrrolidone; and an alcohol such as methanol, ethanol, propanol,n-butanol or tert-butanol.

In a case where T is halogen or —OSO₂G and M is sodium or potassium, thefirst step of the reaction (C) can be carried out usually from 0 to 150°C., preferably from 30 to 110° C. The reaction time is usually fromabout 0.5 to 24 hours, preferably from about 1 to 12 hours.

In a case where T is —OH and M is a hydrogen atom, the first step of thereaction (C) can be carried out usually by Mitsunobu Method. Forexample, it can be carried out by using a dialkyl azo dicarboxylate andtriphenylphosphine in the presence of a solvent. Each of such a dialkylazo dicarboxylate and triphenylphosphine may be used usually in anamount approximately equimolar to the compound of the formula (VI). Theabove dialkyl azo dicarboxylate may, for example, be diethyl azodicarboxylate or diisopropyl azo dicarboxylate.

The solvent may be any solvent so long as it is inert to the reaction.For example, one or more types may suitably be selected for use from,for example, an ether such as diethyl ether, butyl ethyl ether,tetrahydrofuran, dioxane or dimethoxyethane; a halogenated hydrocarbonsuch as chlorobenzene, dichlorobenzene, dichloromethane, chloroform,carbon tetrachloride, dichloroethane, trichloroethane ordichloroethylene; and an aromatic hydrocarbon such as benzene, tolueneor xylene.

In a case where T is —OH and M is a hydrogen atom, the first step of thereaction (C) can be carried out usually from 0 to 80° C., preferablyfrom 20 to 60° C. The reaction time is usually from about 0.5 to 24hours, preferably from about 1 to 16 hours.

The second step of the reaction (C) can be carried out usually bydecomposing the compound of the formula (VIII) by means of hydrazine inthe presence of a solvent. Such hydrazine may be used in an amountapproximately equimolar to the compound of the formula (VIII).

The solvent may be any solvent so long as it is inert to the reaction.For example, one or more types may suitably selected for use from, forexample, an ether such as diethyl ether, butyl ethyl ether,tetrahydrofuran, dioxane or dimethoxyethane; an aromatic hydrocarbonsuch as benzene, toluene or xylene; and an alcohol such as methanol,ethanol, propanol, n-butanol or tert-butanol.

The second step of the reaction (C) can be carried out usually from 0 to140° C., preferably from 30 to 100° C. The reaction time is usually fromabout 0.5 to 24 hours, preferably from about 2 to 12 hours.

Preferred embodiments of pesticides containing the compounds of thepresent invention will be described below. The pesticides containing thecompounds of the present invention are particularly useful, for example,as agents for controlling various pests which become problematic in theagricultural and horticultural fields, i.e. agricultural andhorticultural pesticides, or as agents for controlling pests which areparasitic on animals i.e. pesticides against parasites on animals.

The agricultural and horticultural pesticides containing the compoundsof the present invention are useful as an insecticide, a miticide, anematicide and a soil pesticide, and they are effective for controllingplant parasitic mites such as two-spotted spider mite (Tetranychusurticae), carmine spider mite (Tetranychus cinnabarinus), kanzawa spidermite (Tetranychus kanzawai), citrus red mite (Panonychus citri),European red mite (Panonychus ulmi), broad mite (Polyphagotarsonemuslatus), pink citrus rust mite (Aculops pelekassi) and bulb mite(Rhizoglyphus echinopus); agricultural insect pests such as diamondbackmoth (Plutella xylostella), cabbage armyworm (Mamestra brassicae),common cutworm (Spodoptera litura), codling moth (Laspeyresiapomonella), bollworm (Heliothis zea), tobacco budworm (Heliothisvirescens), gypsy moth (Lymantria dispar), rice leafroller(Cnaphalocrocis medinalis), Adoxophyes sp., summer fruit tortrix(Adoxophyes orana fasciata), peach fruit moth (Carposina niponensis),oriental fruit moth (Grapholita molesta), black cutworm (Agrotisipsilon), cutworm (Agrotis segetum), colorado potato beetle(Leptinotarsa decemlineata), cucurbit leaf beetle (Aulacophorafemoralis), boll weevil (Anthonomus grandis), aphids, planthoppers,leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiidflies, scarabs, ants, leafminer flies; plant parasitic nematodes such asroot-knot nematodes, cyst nematodes, root-lesion nematodes, ricewhite-tip nematode (Aphelenchoides besseyi), strawberry bud nematode(Nothotylenchus acris), pine wood nematode (Bursaphelenchus lignicolus);gastropods such as slugs and snails; soil pests such as isopods such aspillbugs (Armadilidium vulgare) and pillbugs (Porcellio scaber);hygienic insect pests such as tropical rat mite (Ornithonyssus bacoti),housefly (Musca domestica), house mosquito (Culex pipiens) andcockroachs; stored grain insect pests such as angoumois grai moth(Sitotroga cerealella), adzuki bean weevil (Callosobruchus chinensis),red flour beetle (Tribolium castaneum) and mealworms; clothes, house andhousehold insect pests such as casemaking clothes moth (Tineapellionella), black carpet beetle (Anthrenus scrophularidae) andsubterranean termites; domestic mites such as mold mite (Tyrophagusputrescentiae), Dermatophagoides farinae and Chelacaropsis moorei. Amongthem, the agricultural and horticultural pesticides containing thecompounds of the present invention are particularly effective forcontrolling plant parasitic mites, agricultural insect pests, plantparasitic nematodes or the like. Further, they are effective againstinsect pests having acquired resistance to organophosphorus, carbamateand/or synthetic pyrethroid insecticides. Moreover, the compounds of thepresent invention have excellent systemic properties, and by theapplication of the compounds of the present invention to soil treatment,not only noxious insects, noxious mites, noxious nematodes, noxiousgastropods and noxious isopods in soil but also foliage pests can becontrolled.

Another preferred embodiments of the pesticides containing compounds ofthe present invention may be agricultural and horticultural pesticideswhich collectively control the above-mentioned plant parasitic mites,agricultural insect pests, plant parasitic nematodes, gastropods andsoil pests.

The agricultural and horticultural pesticide containing the compound ofthe present invention, is usually formulated by mixing the compound withvarious agricultural adjuvants and used in the form of a formulationsuch as a dust, granules, water-dispersible granules, a wettable powder,a water-based suspension concentrate, an oil-based suspensionconcentrate, water soluble granules, an emulsifiable concentrate, asoluble concentrate, a paste, an aerosol or an ultra low-volumeformulation. However, so long as it is suitable for the purpose of thepresent invention, it may be formulated into any type of formulationwhich is commonly used in this field. Such agricultural adjuvantsinclude solid carriers such as diatomaceous earth, slaked lime, calciumcarbonate, talc, white carbon, kaoline, bentonite, a mixture ofkaolinite and sericite, clay, sodium carbonate, sodium bicarbonate,mirabilite, zeolite and starch; solvents such as water, toluene, xylene,solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone,chlorobenzene, cyclohexane, dimethylsulfoxide, N,N-dimethylformamide,dimethylacetamide, N-methyl-2-pyrrolidone, and alcohol; anionicsurfactants and spreaders such as a salt of fatty acid, a benzoate, analkylsulfosuccinate, a dialkylsulfosuccinate, a polycarboxylate, a saltof alkylsulfuric acid ester, an alkyl sulfate, an alkylaryl sulfate, analkyl diglycol ether sulfate, a salt of alcohol sulfuric acid ester, analkyl sulfonate, an alkylaryl sulfonate, an aryl sulfonate, a ligninsulfonate, an alkyldiphenyl ether disulfonate, a polystyrene sulfonate,a salt of alkylphosphoric acid ester, an alkylaryl phosphate, astyrylaryl phosphate, a salt of polyoxyethylene alkyl ether sulfuricacid ester, a polyoxyethylene alkylaryl ether sulfate, a salt ofpolyoxyethylene alkylaryl ether sulfuric acid ester, a polyoxyethylenealkyl ether phosphate, a salt of polyoxyethylene alkylaryl phosphoricacid ester, and a salt of a condensate of naphthalene sulfonate withformalin; nonionic surfactants and spreaders such as a sorbitan fattyacid ester, a glycerin fatty acid ester, a fatty acid polyglyceride, afatty acid alcohol polyglycol ether, acetylene glycol, acetylenealcohol, an oxyalkylene block polymer, a polyoxyethylene alkyl ether, apolyoxyethylene alkylaryl ether, a polyoxyethylene styrylaryl ether, apolyoxyethylene glycol alkyl ether, a polyethylene glycol, apolyoxyethylene fatty acid ester, a polyoxyethylene sorbitan fatty acidester, a polyoxyethylene glycerin fatty acid ester, a polyoxyethylenehydrogenated castor oil, and a polyoxypropylene fatty acid ester; andvegetable and mineral oils such as olive oil, kapok oil, castor oil,palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice branoil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil,tung oil, and liquid paraffins. Each of the components as such adjuvantsmay be one or more suitably selected for use, so long as the purpose ofthe present invention can thereby be accomplished. Further, variousadditives which are commonly used, such as a filler, a thickener, ananti-settling agent, an anti-freezing agent, a dispersion stabilizer, aphytotoxicity reducing agent, and an anti-mold agent, may also beemployed.

The weight ratio of the compound of the present invention to the variousagricultural adjuvants is usually from 0.001:99.999 to 95:5, preferablyfrom 0.005:99.995 to 90:10.

In the actual application of such a formulation, it may be used as itis, or may be diluted to a predetermined concentration with a diluentsuch as water, and various spreaders e.g. surfactants, vegetable oils ormineral oils may be added thereto, as the case requires.

The application of the agricultural and horticultural pesticidecontaining the compound of the present invention can not generally bedefined, as it varies depending upon the weather conditions, the type ofthe formulation, the application season, the application site or thetypes or degree of outbreak of the pest insects. However, it is usuallyapplied in a concentration of the active ingredient being from 0.05 to800,000 ppm, preferably from 0.5 to 500,000 ppm, and the dose per unitarea is such that the compound of the present invention is from 0.05 to50,000 g, preferably from 1 to 30,000 g, per hectare. Further,agricultural and horticultural pesticides as another preferredembodiment of pesticides containing the compounds of the presentinvention may be applied in accordance with the above-describedapplication of pesticides. The present invention includes such a methodfor controlling pests, particularly for controlling plant parasiticmites, agricultural insect pests or plant parasitic nematodes by suchapplications.

Various formulations of agricultural and horticultural pesticidescontaining the compounds of the present invention or their dilutedcompositions may be applied by conventional methods for applicationwhich are commonly employed, such as spraying (e.g. spraying, jetting,misting, atomizing, powder or grain scattering or dispersing in water),soil application (e.g. mixing or drenching), surface application (e.g.coating, powdering or covering) or impregnation to obtain poisonousfeed. Further, it is possible to feed domestic animals with a foodcontaining the above active ingredient and to control the outbreak orgrowth of pests, particularly insect pests, with their excrements.Furthermore, the active ingredient may also be applied by a so-calledultra low-volume application method. In this method, the composition maybe composed of 100% of the active ingredient.

Further, the agricultural and horticultural pesticides containingcompounds of the present invention may be mixed with or may be used incombination with other agricultural chemicals, fertilizers orphytotoxicity-reducing agents, whereby synergistic effects or activitiesmay sometimes be obtained. Such other agricultural chemicals include,for example, a herbicide, an insecticide, a miticide, a nematicide, asoil pesticide, a fungicide, an antivirus agent, an attractant, anantibiotic, a plant hormone and a plant growth regulating agent.Especially, with a mixed pesticide having a compound of the presentinvention mixed with or used in combination with one or more activecompounds of other agricultural chemicals, the application range, theapplication time, the pesticidal activities, etc. may be improved topreferred directions. The compound of the present invention and theactive compounds of other agricultural chemicals may separately beformulated so that they may be mixed for use at the time of application,or they may be formulated together. The present invention includes sucha mixed pesticidal composition.

The mixing ratio of the compound of the present invention to the activecompounds of other agricultural chemicals can not generally be defined,since it varies depending upon the weather conditions, the types offormulations, the application time, the application site, the types ordegree of outbreak of insect pests, etc., but it is usually within arange of from 1:300 to 300:1, preferably from 1:100 to 100:1, by weight.Further, the dose for the application is such that the total amount ofthe active compounds is from 0.1 to 50,000 g, preferably from 1 to30,000 g, per hectare. The present invention includes a method forcontrolling pests by an application of such a mixed pesticidecomposition.

The active compounds of insect pest control agents such as insecticides,miticides, nematicides or soil pesticides in the above-mentioned otheragricultural chemicals, include, for example, (by common names, some ofthem are still in an application stage) organic phosphate compounds suchas Profenofos, Dichlorvos, Fenamiphos, Fenitrothion, EPN, Diazinon,Chlorpyrifos-methyl, Acephate, Prothiofos, Fosthiazate, Phosphocarb,Cadusafos, Disulfoton, Chlorpyrifos, Demeton-S-methyl, Dimethoate,Methamidophos and Parathion; carbamate compounds such as Carbaryl,Propoxur, Aldicarb, Carbofuran, Thiodicarb, Methomyl, Oxamyl,Ethiofencarb, Pirimicarb, Fenobucarb, Carbosulfan, and Benfuracarb;nereistoxin derivatives such as Cartap, and Thiocyclam, and Bensultap;organic chlorine compounds such as Dicofol, Tetradifon and Endosulfan;organometallic compounds such as Fenbutatin Oxide; pyrethroid compoundssuch as Fenvalerate, Permethrin, Cypermethrin, Deltamethrin,Cyhalothrin, Tefluthrin, Ethofenprox, Fenpropathrin and Bifenthrin;benzoylurea compounds such as Diflubenzuron, Chlorfluazuron,Teflubenzuron, Flufenoxuron, Lufenuron, Novaluron, Bistrifluron andNoviflumuron; juvenile hormone-like compounds such as Methoprene,Pyriproxyfen, and Fenoxycarb; pyridazinone compounds such as Pyridaben;pyrazole compounds such as Fenpyroximate, Fipronil, Tebufenpyrad,Ethiprole, Tolfenpyrad, Acetoprole, Pyrafluprole and Pyriprole;neonicotinoids such as Imidacloprid, Nitenpyram, Acetamiprid,Thiacloprid, Thiamethoxam, Clothianidin, and Dinotefuran; hydrazinecompounds such as Tebufenozide, Methoxyfenozide, Chromafenozide andHalofenozide; dinitro compounds; organic sulfur compounds; ureacompounds; triazine compounds; hydrazone compounds; and other compounds,such as Flonicamid, Buprofezin, Hexythiazox, Amitraz, Chlordimeform,Silafluofen, Triazamate, Pymetrozine, Pyrimidifen, Chlorfenapyr,Indoxacarb, Acequinocyl, Etoxazole, Cyromazine, 1,3-dichloropropene,Diafenthiuron, Benclothiaz, Flufenerim, Pyridalyl, Spirodiclofen,Bifenazate, Spiromesifen, Propargite, Clofentezine, Fluacrypyrim,Flubendiamide, Cyflumetofen, Metaflumizone and Amidoflumet. Further,microbial agricultural chemicals such as BT agents, insect viruses,entomopathogenic fungi, and nematophagous fungi, antibiotics such asAvermectin, Emamectin-Benzoate, Milbemectin, Spinosad, Ivermectin andLepimectin or natural products such as Azadirachtin, and Rotenone, maybe used in admixture or in combination. The active compounds offungicides among the above-mentioned other agricultural chemicalsinclude, for example, (by common names, some of which are still in anapplication stage) pyrimidinamine compounds such as Mepanipyrim,Pyrimethanil, and Cyprodinil; azole compounds such as Triadimefon,Bitertanol, Triflumizole, Etaconazole, Propiconazole, Penconazole,Flusilazole, Myclobutanil, Cyproconazole, Terbuconazole, Hexaconazole,Furconazole-cis, Prochloraz, Metconazole, Epoxiconazole, Tetraconazole,Oxpoconazole, and Sipconazole; quinoxaline compounds such asQuinomethionate; dithiocarbamate compounds such as Maneb, Zineb,Mancozeb, Polycarbamate, Propineb; organic chlorine compounds such asFthalide, Chlorothalonil, and Quintozene; imidazole compounds such asBenomyl, Thiophanate-Methyl, Carbendazim, and Cyazofamid; pyridinaminecompounds such as Fluazinam; cyanoacetamide compounds such as Cymoxanil;phenylamide compounds such as Metalaxyl, Oxadixyl, Ofurace, Benalaxyl,Furalaxyl, and Cyprofuram; sulfenic acid compounds such asDichlofluanid; copper compounds such as cupric hydroxide, and OxineCopper; isoxazole compounds such as Hydroxyisoxazole; organophosphoruscompounds such as Fosetyl-Al, Tolclofos-Methyl, S-benzylO,O-diisopropylphosphorothioate, O-ethyl S,S-diphenylphosphorodithioate,and aluminumethylhydrogen phosphonate; N-halogenothioalkyl compoundssuch as Captan, Captafol, and Folpet; dicarboximide compounds such asProcymidone, Iprodione, and Vinclozolin; benzanilide compounds such asFlutolanil, Mepronil, and Zoxamide; piperazine compounds such asTriforine; pyridine compounds such as Pyrifenox; carbinol compounds suchas Fenarimol; and Flutriafol; piperidine compounds such as Fenpropidine;morpholine compounds such as Fenpropimorph; organotin compounds such asFentin Hydroxide, and Fentin Acetate; urea compounds such as Pencycuron;cinnamic acid compounds such as Dimethomorph; phenylcarbamate compoundssuch as Diethofencarb; cyanopyrrole compounds such as Fludioxonil, andFenpiclonil; Strobilurin compounds such as Azoxystrobin,Kresoxim-Methyl, Metominofen, Trifloxystrobin, Picoxystrobin, andPyraclostrobin; oxazolidinedione compounds such as Famoxadone; thiazolecarboxamide compounds such as Ethaboxam; silyl amide compounds such asSilthiopham; aminoacid amidecarbamate compounds such as Iprovalicarb;imidazolidine compound such as Fenamidone; hydroxyanilide compounds suchas Fenhexamid; benzene sulfonamide compounds such as Flusulfamide;anthraquinone compounds; crotonic acid compounds; antibiotics; and othercompounds, such as Isoprothiolane, Tricyclazole, Pyroquilon,Diclomezine, Probenazole, Quinoxyfen, Propamocarb Hydrochloride,Spiroxamine, Chloropicrin, Dazomet, and Metam-Sodium.

Further, agricultural chemicals which may be used in admixture with orin combination with the compounds of the present invention, may, forexample, be the active ingredient compounds in the herbicides asdisclosed in Farm Chemicals Handbook (2002 edition), particularly thoseof soil treatment type.

The pesticides against parasites on animals are effective forcontrolling e.g. external parasites which are parasitic on the bodysurface of host animals (such as the back, the axilla, the lower abdomenor inside of the thigh) or internal parasites which are parasitic in thebody of host animals (such as the stomach, the intestinal tract, thelung, the heart, the liver, the blood vessels, the subcutis or lymphatictissues), but they are particularly effective for controlling theexternal parasites.

The external parasites may, for example, be animal parasitic acarina orfleas. Their species are so many that it is difficult to list all ofthem, and therefore, their typical examples will be given.

The animal parasitic acarina may, for example, be ticks such asBoophilus microplus, Rhipicephalus sanguineus, Haemaphysalislongicornis, Haemaphysalis flava, Haemaphysalis campanulata,Haemaphysalis concinna, Haemaphysalis japonica, Haemaphysalis kitaokai,Haemaphysalis ias, Ixodes ovatus, Ixodes nipponensis, Ixodespersulcatus, Amblyomma testudinarium, Haemaphysalis megaspinosa,Dermacentor reticulatus, and Dermacentor taiwanesis; common red mite(Dermanyssus gallinae); northern fowl mites such as Ornithonyssussylviarum, and Ornithonyssus bursa; trombidioids such as Eutrombiculawichmanni, Leptotrombidium akamushi, Leptotrombidium pallidum,Leptotrombidium fuji, Leptotrombidium tosa, Neotrombicula autumnalis,Eutrombicula alfreddugesi, and Helenicula miyagawai; cheyletidae such asCheyletiella yasguri, Cheyletiella parasitivorax, and Cheyletiellablakei; sarcoptic mange mites such as Psoroptes cuniculi, Chorioptesbovis, Otodectes cynotis, Sarcoptes scabiei, and Notoedres cati; andDemodicidae such as Demodex canis. The pesticides against parasites onanimals, containing the compounds of the present invention, areparticularly effective for the control of ticks among them.

The fleas may, for example, be externally parasitic wingless insectsbelonging to Siphonaptera, more specifically, fleas belonging toPulicidae, Ceratephyllus, etc. Fleas belonging to Pulicidae may forexample, be Ctenocephalides canis, Ctenocephalides felis, Pulexirritans, Echidnophaga gallinacea, Xenopsylla cheopis, Leptopsyllasegnis, Nosopsyllus fasciatus, and Monopsyllus anisus. The pesticidesagainst parasites on animals, containing the compounds of the presentinvention, are particularly effective for the control of fleas belongingto Pulicidae, particularly Ctenocephalides canis and Ctenocephalidesfelis, among them.

Other external parasites may, for example, be sucking lice (Anoplura)such as shortnosed cattle louse (Haematopinus eurysternus), horsesucking louse (Haematopinus asini), sheep louse, longnosed cattle louse(Linognathus vituli), and head louse (Pediculus capitis); biting licesuch as dog biting louse (Trichodectes canis); and blood-suckingdipterous insects such as horsefly (Tabanus trigonus), biting midges(Culicoides schultzei), and blackfly (Simulium ornatum). Further, theinternal parasites may, for example, be nematodes such as lung worms,whipworms (Trichuris), tuberous worms, gastric parasites, ascaris, andfilarioidea; cestoda such as Spirometra erinacei, Diphyllobothriumlatum, Dipylidium caninum, Taenia multiceps, Echinococcus granulosus,Echinococcus multilocularis, trematoda such as Schistosoma japonicum,Fasciola hepatica; and protozoa such as coccidia, malaria parasites(Plasmodium malariae), intestinal sarcocyst, toxoplasma, andcryptosporidium.

The host animals may, for example, be pet animals, domestic animals, andpoultry, such as dogs, cats, mice, rats, hamsters, guinea pigs,squirrels, rabbits, ferrets, birds (such as pigeons, parrots, hillmynas, Java sparrows, honey parrots, lovebirds and canaries), cows,horses, pigs, sheep, ducks and chickens. The pesticides againstparasites on animals, containing the compounds of the present invention,are particularly effective for the control of pests parasitic on petanimals or domestic animals, especially for the control of externalparasites, among them. Among pet animals or domestic animals, they areeffective particularly for dogs, cats, cows and horses.

When the compound of the present invention is used as a pesticideagainst parasites on animals, it may be used as it is or may be usedtogether with suitable adjuvants, as formulated into variousformulations such as a dust, granules, tablets, a powder, capsules, asoluble concentrate, an emulsifiable concentrate, a water-basedsuspension concentrate and an oil-based suspension concentrate. Inaddition to such formulations, it may be formulated into any type offormulation which is commonly used in this field, so long as it issuitable for the purpose of the present invention. The adjuvants to beused for formulations may, for example, be anionic surfactants ornonionic surfactants exemplified above as adjuvants for formulation ofagricultural and horticultural pesticides; a cationic surfactant such ascetyl trimethylammonium bromide; a solvent such as water, acetone,acetonitrile, monomethylacetamide, dimethylacetamide, dimethylformamide,2-pyrrolidone, N-methyl-2-pyrrolidone, kerosene, triacetin, methanol,ethanol, isopropanol, benzyl alcohol, ethylene glycol, propylene glycol,polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol,ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,diethylene glycol monoethyl ether, diethylene glycol n-butyl ether,dipropylene glycol monomethyl ether, or dipropylene glycol n-butylether; an antioxidant such as butylhydroxyanisole, butylhydroxytoluene,ascorbic acid, sodium hydrogenmetasulfite, propyl gallate or sodiumthiosulfate; a coating film-forming agent such as polyvinylpyrrolidone,polyvinyl alcohol, or a copolymer of vinyl acetate and vinylpyrrolidone; the vegetable oils and mineral oils as exemplified above asadjuvants for formulation of agricultural and horticultural pesticides;and a carrier such as lactose, sucrose, glucose, starch, wheat flour,corn powder, soybean cake and meal, defatted rice bran, calciumcarbonate or other commercially available feed materials. One or more ofthe respective components of these adjuvants may be suitably selectedfor use, so long as such will not depart from the purpose of the presentinvention. Further, other than the above-mentioned adjuvants, some amongthose known in this field may suitably be selected for use, and stillfurther, some among the above-mentioned various adjuvants to be used inthe agricultural and horticultural field may suitably be selected foruse.

The blend ratio of the compound of the present invention to variousadjuvants is usually from 0.1:99.9 to 90:10. In the actual use of such aformulation, it may be used as it is, or may be diluted to apredetermined concentration with a diluent such as water, and variousspreaders (e.g. surfactants, vegetable oils or mineral oils) may beadded thereto, as the case requires.

Administration of the compound of the present invention to a host animalis carried out orally or parenterally. As an oral administration method,a method of administering a tablet, a liquid agent, a capsule, a wafer,a biscuit, a minced meat or other feed, containing the compound of thepresent invention, may be mentioned. As a parenteral administrationmethod, there may, for example, be mentioned a method wherein thecompound of the present invention is formulated into a suitableformulation and then taken into the body by e.g. intravenousadministration, intramuscular administration, intradermaladministration, hypodermic administration, etc.; a method wherein it isadministered on the body surface by spot-on treatment, pour-on treatmentor spray treatment; or a method of embedding a resin fragment or thelike containing the compound of the present invention under the skin ofthe host animal.

The dose of the compound of the present invention to a host animalvaries depending upon the administration method, the purpose ofadministration, the diseased symptom, etc., but it is usuallyadministered in a proportion of from 0.01 mg to 100 g, preferably from0.1 mg to 10 g, per 1 kg of the body weight of the host animal.

The present invention also includes a method for controlling a pest bythe above-mentioned administration method or by the above-mentioneddose, particularly a method for controlling external parasites orinternal parasites.

Further, in the present invention, there may be a case where bycontrolling pests parasitic on animals as described above, it ispossible to prevent or cure various diseases of the host animal therebycaused. Thus, the present invention also includes a preventive ortherapeutic agent for an animal disease caused by parasite, containingthe compound of the present invention as an active ingredient, and amethod for preventing or curing an animal disease caused by parasite.

When the compound of the present invention is used as a pesticideagainst parasites on animals, various vitamins, minerals, amino acids,nutrients, enzymes, antipyretics, sedatives, antiphlogistics,fungicides, colorants, aromatic substances, preservatives, etc., may beused in admixture with or in combination with the adjuvants. Further, asthe case requires, other animal drugs or agricultural chemicals, such asvermicides, anti-coccidium agents, insecticides, miticides, pulicides,nematocides, bactericides or antibacterial agents, may be mixed orcombined for use, whereby improved effects may sometimes be obtained.The present invention includes such a mixed pesticidal compositionhaving the above-mentioned various components mixed or combined for use,and further a method for controlling a pest by using it, particularly amethod for controlling external parasites or internal parasites.

Now, some of preferred embodiments of the compounds of the presentinvention will be exemplified. Among the exemplified, with respect tothe following (1) to (8), optional two or more may suitably be combined,and compounds based on such combinations are also preferred embodimentsof the compounds of the present invention. Further, pesticides,agricultural and horticultural pesticides, insecticides, miticides,nematicides, pesticides against parasites on animals, pesticides againstexternal parasites on animals and preventive or therapeutic agents foranimal diseases caused by parasites, containing the following compoundsas active ingredients, are also preferred embodiments in the presentinvention. Further, methods for controlling pests thereby applyingeffective amounts of the following compounds, are also preferredembodiments in the present invention. However, it should be understoodthat the present invention is by no means thereby restricted.

(1) A compound of the above formula (I) wherein at least one of R¹ issubstituted at the 4-position, and such R¹ is a fluorine atom or achlorine atom.

(2) A compound of the above formula (I) wherein at least one of R¹ issubstituted at the 4-position, and such R¹ is a chlorine atom.

(3) A compound of the above formula (I) wherein at least one of R¹ issubstituted at the 4-position, and such R¹ is alkyl, haloalkyl, alkenyl,haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenoxy carbonylwhich may be substituted, nitro or formyl.

(4) A compound of the above formula (I) wherein R² is halogen, haloalkylor haloalkoxy.

(5) A compound of the above formula (I) wherein R³ is halogen.

(6) A compound of the above formula (I) wherein R³ is halogen and 3- or5-monosubstituted, or 3,5-disubstituted.

(7) A compound of the above formula (I) wherein Y is cyclopropyl.

(8) A compound of the above formula (I) wherein Y is cyclopropyl, andsuch cyclopropyl is substituted by 1 to 5 substituents selected from thegroup consisting of halogen, alkyl and haloalkyl.

(9) A compound of the above formula (I) wherein R¹ is halogen, alkyl,haloalkyl, alkylcarbonyl or formyl; R² is halogen, haloalkyl orhaloalkoxy; R³ is halogen or haloalkyl; A is alkyl substituted by Y; Yis cyclopropyl which may be substituted by at least one substituentselected from the group consisting of halogen and alkyl; m is 1 or 2; nis 0; and q is 1.

(10) A compound as defined in the above (9), wherein R¹ is2-monosubstituted or 2,4-disubstituted, and R³ is 3-monosubstituted.

(11) A compound of the above formula (I) wherein R¹ is halogen, alkyl orhaloalkyl, R² is halogen, haloalkyl or haloalkoxy, R³ is halogen, A isalkyl substituted by Y, Y is cyclopropyl, m is 2, n is 0, and q is 1.

(12) A compound as defined in the above (11) wherein R¹ is2,4-disubstituted, and R³ is 3-monosubstituted.

(13) A compound as defined in the above (12) wherein R¹ at the4-position is a chlorine atom.

(14) A compound of the formula (I) which is represented by the formula(I-1):

wherein R^(1a) is halogen or alkyl; each of R^(1b) and R^(1d) is ahydrogen atom; R^(1c) is alkyl, haloalkyl, alkenyl, haloalkenyl,alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylcarbonyl,haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, phenoxycarbonylwhich may be substituted, nitro or formyl; R² is halogen, haloalkyl orhaloalkoxy; R^(3a) is halogen or haloalkyl; each of R^(3b), R^(3c) andR^(3d) is a hydrogen atom; A is alkyl substituted by Y;

Y is cyclopropyl which may be substituted by 1 to 5 substituentsselected from the group consisting of halogen, alkyl and haloalkyl; andn is 0.

(15) A compound as defined in the above (14) wherein R^(1c) ishaloalkyl, alkylcarbonyl or formyl.

(16) A compound as defined in the above (14) wherein R^(1c) ishaloalkyl.

(17) A compound as defined in the above (14) wherein Y is cyclopropyl.

(18) A compound of the formula (I) which is represented by the formula(Ia):

wherein R¹ is halogen or alkyl; each of R² and R³ is halogen or —CF₃; Ais alkyl substituted by Y; Y is C₃₋₄ cycloalkyl which may be substitutedby halogen or alkyl; m is 1 or 2; and n is 0 or 1.

(19) A compound of the formula (I) which is represented by the aboveformula (Ia) wherein R¹ is halogen or alkyl; each of R² and R³ which areindependent of each other is halogen or —CF₃; A is —X—Y; X is alkylene;Y is C₃₋₄ cycloalkyl which may be substituted by halogen or alkyl; m is1 or 2; and n is 0 or 1.

EXAMPLES

Now, the present invention will be described with reference to Examples,but it should be understood that the present invention is by no meanslimited thereto. Firstly, Preparation Examples of the compound of thepresent invention will be described.

Preparation Example 1

Preparation ofN-[6-[[(cyclopropylmethyl)amino]carbonyl]-2-methylphenyl]-1-(3-chloro-2-pyridyl)-3-(trifluoromethyl)-1H-pyrazol-5-carboxamide(after-mentioned compound No. 1) 1.49 g of triethylamine was graduallydropwise added to a mixed solution comprising 0.8 g ofcyclopropylmethylamine hydrochloride and 40 ml of tetrahydrofuran undercooling with ice, followed by stirring at room temperature for 30minutes. Then, a mixed solution comprising 1 g of2-[1-(3-chloro-2-pyridyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]-8-methyl-4H-3,1-benzoxazin-4-oneand 10 ml of tetrahydrofuran was gradually dropwise added. Aftercompletion of the dropwise addition, the mixed solution was reacted for4 hours under reflux. After completion of the reaction, the solvent wasdistilled off under reduced pressure, and to the residue, ethyl acetateand water were added for extraction. The organic layer was washed withwater and a saturated sodium chloride aqueous solution and dried overanhydrous magnesium sulfate. The solvent was distilled off under reducedpressure, and the residue was purified by silica gel columnchromatography (eluent: n-hexane/ethyl acetate=1/1) to obtain 0.54 g ofthe desired product having a melting point of 199.4° C.

Preparation Example 2

Preparation ofN-[4-chloro-2-methyl-6-[[α-methyl-(cyclopropylmethyl)amino]carbonyl]-phenyl]-3-(trifluoromethyl)-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-carboxamide(after-mentioned compound No. 3)

1.37 g of triethylamine was gradually dropwise added to a mixed solutioncomprising 0.82 g of α-methyl-cyclopropylmethylamine hydrochloride and40 ml of tetrahydrofuran under cooling with ice, followed by stirring atroom temperature for 30 minutes. Then, a mixed solution comprising 1 gof2-[1-(3-chloro-2-pyridyl)-3-(trifluoromethyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazin-4-oneand 10 ml of tetrahydrofuran were gradually dropwise added. Aftercompletion of the dropwise addition, the mixed solution was reacted for4 hours under reflux. After completion of the reaction, the solvent wasdistilled off under reduced pressure, and to the residue, ethyl acetateand water were added for extraction. The organic layer was washed withwater and a saturated sodium chloride aqueous solution and dried overanhydrous magnesium sulfate. The solvent was distilled off under reducedpressure, and the residue was purified by silica gel columnchromatography (eluent: n-hexane/ethyl acetate=1/1) to obtain 0.45 g ofthe desired product having a melting point of 210.0° C.

Preparation Example 3

Preparation ofN-[4-chloro-2-methyl-6-[[α-methyl-(cyclopropylmethyl)amino]carbonyl]-phenyl]-3-bromo-l-(3-chloro-2-pyridyl)-1H-pyrazol-5-carboxamide(after-mentioned compound No. 9)

1.07 g of triethylamine was gradually dropwise added to a mixed solutioncomprising 0.65 g of α-methyl-cyclopropylmethylamine hydrochloride and40 ml of tetrahydrofuran under cooling with ice, followed by stirring atroom temperature for 30 minutes. Then, a mixed solution comprising 0.8 gof2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-chloro-8-methyl-4H-3,1-benzoxazin-4-oneand 10 ml of tetrahydrofuran was gradually dropwise added. Aftercompletion of the dropwise addition, the mixed solution was reacted for4 hours under reflux. After completion of the reaction, the solvent wasdistilled off under reduced pressure, and to the residue, ethyl acetateand water were added for extraction. The organic layer was washed withwater and a saturated sodium chloride aqueous solution and dried overanhydrous magnesium sulfate. The solvent was distilled off under reducedpressure, and the residue was purified by silica gel columnchromatography (eluent: n-hexane/ethyl acetate=1/1) to obtain 0.33 g ofthe desired product having a melting point of 183.6° C.

Prepartaion Example 4

Preparation ofN-[2-bromo-4-chloro-6-[[α-methyl-(cyclopropylmethyl)amino]carbonyl]-phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-carboxamide(after-mentioned compound No. 15) 1 g of triethylamine was graduallydropwise added to a mixed solution comprising 0.6 g ofα-methyl-cyclopropylmethylamine hydrochloride and 40 ml oftetrahydrofuran under cooling with ice, followed by stirring for 1 hourat room temperature. Then, a mixed solution comprising 0.85 g of2-[3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazol-5-yl]-6-chloro-8-bromo-4H-3,1-benzoxazin-4-oneand 10 ml of tetrahydrofuran was gradually dropwise added. Aftercompletion of the dropwise addition, the mixed solution was reacted for4 hours under reflux. After completion of the reaction, the solvent wasdistilled off, and to the residue, ethyl acetate and water were addedfor extraction. The organic layer was washed with water and a saturatedsodium chloride aqueous solution and dried over anhydrous magnesiumsulfate. The solvent was distilled off under reduced pressure, and theresidue was purified by silica gel column chromatography (eluent:n-hexane/ethyl acetate=1/2) to obtain 0.7 g of the desired producthaving a melting point of 260.6° C.

Now, typical examples of the compound of the present inventionrepresented by the above formula (I) will be given in Table 1. Thesecompounds can be prepared by the above-described Preparation Examples orby the above-mentioned various processes for the production of thecompound of the present invention.

In Table 1, No. represents compound No. Further, in Table 1, Merepresents a methyl group, Et an ethyl group, iPr an isopropyl group,CPr a cyclopropyl group, CBu a cyclobutyl group, and Ph a phenyl group.Further, in Table 1, Al represents —CH₂—[CPr], A2 —CH(Me)-[CPr], A3—CH₂-[2-Me-CPr], A4 —CH₂-[2,2-Cl₂-1-Me-CPr], A5 —CH₂-[1-Me-CPr], and A6—CH (Me)-[CBu]. Further, in Table 1, 2-Me-CPr represents a cyclopropylgroup having a methyl group substituted at the 2-position, andCO₂Ph(4-Cl) represents a phenoxycarbonyl group having a chlorine atomsubstituted at the 4-position of the phenyl group. The same applies toother similar descriptions.

Further, in Table 1, n is 0 unless otherwise specified.

TABLE 1 (I-1)

Physical properties No. R^(1a) R^(1b) R^(1c) R^(1d) R² R^(3a) R^(3b)R^(3c) R^(3d) A (mp: °C.) 1 Me H H H CF₃ Cl H H H A1 199.4 2 Me H Cl HCF₃ Cl H H H A1 216.4 3 Me H Cl H CF₃ Cl H H H A2 210.0 4 Me H Cl H CF₃Cl H H H A3 5 Me H Cl H CF₃ Cl H H H A4 219.3 6 Me H Cl H Cl Cl H H H A17 Me H Cl H Br Cl H H H A1 8 Me H Cl H Cl Cl H H H A2 186.7 9 Me H Cl HBr Cl H H H A2 183.6 10 Me H Cl H CF₃ Cl H H H A5 161.2 11 Br H Cl H CF₃Cl H H H A2 158.2 12 I H Br H CF₃ Cl H H H A2 145.5 13 Me H Cl H CF₃ ClH H H A2 230.9 14 Cl H Cl H CF₃ Cl H H H A2 238.8 15 Cl H Cl H Br Cl H HH A2 236.8 16 Br H Cl H Br Cl H H H A2 260.6 17 I H Cl H Br Cl H H H A2251.4 18 Br H F H CF₃ Cl H H H A2 220.1 19 I H Cl H CF₃ Cl H H H A2241.0 20 Cl H F H CF₃ Cl H H H A2 214.0 21 I H I H CF₃ Cl H H H A2 251.922 Br H F H Br Cl H H H A2 219.2 23 Me H Cl H CF₃ Br H H H A2 162-164 24Me H Cl H Cl CF₃ H H H A2 154-156 25 Me H Cl H Br Br H H H A2 128-132 26Cl H F H Br Cl H H H A2 27 I H F H Br Cl H H H A2 28 F H Cl H Br Cl H HH A2 29 F H Cl H CF₃ Cl H H H A2 30 I H F H CF₃ Cl H H H A2 31 F H F HCF₃ Cl H H H A2 32 F H F H Br Cl H H H A2 33 Me H F H CF₃ Cl H H H A2 34Me H F H Br Cl H H H A2 35 Me H CO₂Me H Br Cl H H H A2 36 Me H CO₂-iPr HBr Cl H H H A2 37 Me H CO₂Ph H Br Cl H H H A2 38 Br H Cl H Cl Cl H H HA2 233.2 39 Br H F H Cl Cl H H H A2 179.1 40 Me H COCH₃ H CF₃ Cl H H HA2 143.4 41 Me H CHO H CF₃ Cl H H H A2 152.3 42 Me H CHF₂ H CF₃ Cl H H HA2 212.9 43 Me H CHF₂ H Br Cl H H H A2 44 Me H CHF₂ H Cl Cl H H H A2 45Et H Cl H CF₃ Cl H H H A2 215.4 46 Et H Cl H Br Cl H H H A2 47 Et H Cl HCl Cl H H H A2 48 Me H NO₂ H CF₃ Cl H H H A2 197.9 49 Me H NO₂ H Br Cl HH H A2 50 Me H NO₂ H Cl Cl H H H A2 51 Me H CF₃ H Br Cl H H H A2 52 Me HCF₃ H Cl Cl H H H A2 53 Me H CF₃ H CF₃ Cl H H H A2 54 CF₃ H Cl H Br Cl HH H A2 55 Me H OMe H Br Cl H H H A2 56 Me H OMe H CF₃ Cl H H H A2 57 MeH OMe H Cl Cl H H H A2 58 OCHF₂ H Cl H Cl Cl H H H A2 59 OCHF₂ H Cl H BrCl H H H A2 60 OCHF₂ H Cl H CF₃ Cl H H H A2 61 CHF₂ H Cl H CF₃ Cl H H HA2 62 CHF₂ H Cl H Br Cl H H H A2 63 CHF₂ H Cl H Cl Cl H H H A2 64 Me HCH═CH₂ H CF₃ Cl H H H A2 65 Me H C≡CH H CF₃ Cl H H H A2 66 Me H Cl H CF₃Cl H H H A6 67 Me H COCF₃ H Br Cl H H H A2 68 Me H CH═CCl₂ H CF₃ Cl H HH A2 69 Me H C≡CI H CF₃ Cl H H H A2 70 Me H CO₂Ph(4-Cl) H Br Cl H H H A271 Me H CO₂Ph(4-Me) H CF₃ Cl H H H A2 72 Me H CO₂Ph(4-NO₂) H CF₃ Cl H HH A2 73 Me H CO₂Ph(4-CN) H CF₃ Cl H H H A2 74 Me H CO₂Ph(4-SMe) H CF₃ ClH H H A2 75 Et H Cl H OCH₂CF₃ Cl H H H A2 76 Me H NO₂ H OCH₂CF₃ Cl H H HA2 77 Me H CHF₂ H CF₃ H H Cl H A2 78 Et H Cl H Br H H F H A2 79 I H Cl HBr F H F H A2 80 I H Cl H Cl Cl H H H A2 220.6 81 Me H Cl H OCH₂CF₃ Cl HH H A2 175.1 82 Br H CHF₂ H CF₃ Cl H H H A2 83 Br H CHF₂ H Br Cl H H HA2 84 Br H CHF₂ H Cl Cl H H H A2 85 Me H Cl H CF₃ Cl H Cl H A2 86 Me HCl H CF₃ Cl H F H A2 87 Br H NO₂ H Br Cl H H H A2 88 Br H NO₂ H CF₃ Cl HH H A2 89 Br H NO₂ H Cl Cl H H H A2 90 I H Br H Cl Cl H H H A2 222.9 91I H Br H Br Cl H H H A2 221.0 92 Me H Me H CF₃ Cl H H H A2 172.3 93 Me HCO₂-iPr H Br Cl H H H A2 176-179 94 Et H Br H CF₃ Cl H H H A2 175.2 95Et H NO₂ H CF₃ Cl H H H A2 116.8 96 Me H CO₂Me H Br Cl H H H A2 190-19897 CF₃ H Cl H Br Cl H H H A2 98 CF₃ H Br H CF₃ Cl H H H A2 234.8 99 CF₃H Cl H CF₃ Cl H H H A2 230.0 100 Cl H CF₃ H Br Cl H H H A2 101 Br H CF₃H CF₃ Cl H H H A2 102 Cl H CF₃ H CF₃ Cl H H H A2 103 N-oxide of compoundNo. 1 (n = 1) 104 N-oxide of compound No. 3 (n = 1) 105 N-oxide ofcompound No. 9 (n = 1) 106 N-oxide of compound No. 16 (n = 1) 107N-oxide of compound No. 22 (n = 1) 108 N-oxide of compound No. 42 (n =1)

Now, test examples will be described.

Test Example 1

Test on Controlling Effects Against Common Cutworm (Spodoptera litura)

A leaf segment of cabbage was dipped for about 10 seconds in aninsecticidal solution prepared to bring the concentration of thecompound of the present invention to 50 ppm or 3.1 ppm and dried in air.A wet filter paper was laid in a petri dish having a diameter of 9 cm,and the dried leaf segment of cabbage was placed thereon. Tensecond-third instar larvae common cutworm were released therein andafter putting a cover, left in a constant temperature chamber at 25° C.with lightening. Dead larvae were counted 5 days after the release, andthe mortality was calculated by the following equation. Here, moribundinsects were counted as dead insects. The mortality at 50 ppm wasobtained with respect to the above-mentioned compound Nos. 8, 20 to 22,25, 41, 91 to 93 and 96, whereby all compounds showed high controllingeffects with a mortality of at least 90%, and the mortality at 3.1 ppmwas obtained with respect to the above-mentioned compound Nos. 1 to 3,5, 9 to 19, 23, 24, 38 to 40, 42, 80, 81 and 90, whereby all compoundsshowed high controlling effects with a mortality of at least 90%.Mortality (%)=(number of dead insects/number of released insects)×100

Test Example 2

Tests on Controlling Effects Against Silverleaf Whitefly (Bemisiaargentifoli)

Adults of silverleaf whitefly were released on cucumber with only onefirst true leaf left and other leaves cut off and planted in a pot, andpermitted to lay eggs for about 8 hours. Thereafter, they were left forfrom 7 to 10 days in a constant temperature chamber at 25° C. withlightening. The number of hatchings was counted, and then, the infestedleaf was dipped for about 10 seconds in an insecticidal solutionprepared to bring the concentration of the compound of the presentinvention to 200 ppm or 50 ppm and dried in air. After the treatment, itwas left in a constant temperature chamber at 25° C. with lightening forfrom 10 to 14 days, whereupon the number of old instar larvae and thenumber of pupae were counted, and the protective value was obtained bythe following equation. The protective value at 200 ppm was obtainedwith respect to the above-mentioned compound Nos. 11 and 21, wherebythey showed high controlling effects with a protective value of at least80%, and the protective value at 50 ppm was obtained with respect to theabove-mentioned compound Nos. 3, 9, 12, 14 to 20, 22, 38 and 39, wherebyall compounds showed high controlling effects with a protective value ofat least 80%.Protective value (%)=(1−((Ta×Cb)/(Tb×Ca)))×100

Ta: The number of old instar larvae+the number of pupae after thetreatment at the treated section

Tb: The number of hatchings before the treatment at the treated section

Ca: The number of old instar larvae+the number of pupae after thetreatment at untreated section

Cb: the number of hatching before the treatment at the untreated section

Test Example 3

Test on Controlling Effects Against Green Peach Aphid (Myzus persicae)

The petiole of eggplant with only one true leaf left and planted in apot, was coated with a sticker, and then about 2-3 apterous viviparousfemales of green peach aphid were released on the true leaf. After twodays from the release, the adult insects were removed, and the number oflarvae was counted. Then, the leaf of the eggplant infested with thelarvae was dipped in an insecticidal solution prepared to bring theconcentration of the compound of the present invention to 800 ppm, forabout 10 seconds, then dried in air and left in a constant temperaturechamber at 25° C. with lightening. The number of survived insects wascounted 5 days after the treatment, and the mortality was calculated bythe following equation. The mortality was obtained with respect to theabove-mentioned compound Nos. 2, 9, 11, 14 to 18, 20, 22, 23, 38, 39, 42and 90, whereby all compounds showed high controlling effects with amortality of at least 90%.Mortality (%)=(1−(number of survived insects/number of treatedinsects))×100

Test Example 4

Test on Controlling Effects Against Cotton Aphid (Aphis gossypii)

The petiole of eggplant with only one true leaf left and planted in apot, was coated with a sticker, and then about 3-4 apterous viviparousfemales of cotton aphid were released on the true leaf. After two daysfrom the release, the adult insects were removed, and the number oflarvae was counted. The leaf of eggplant infested with the larvae wasdipped in an insecticidal solution prepared to bring the concentrationof the compound of the present invention to 50 ppm, for about 10seconds, then dried in air and left in a constant temperature chamber at25° C. with lightening. The number of survived insects was counted 5days after the treatment, and the mortality was obtained in the samemanner as in the above Test Example 3. The mortality was obtained withrespect to the above-mentioned compound Nos. 16, 18 and 22, whereby allcompounds showed high controlling effects with a mortality of at least90%.

Test Example 5

Test on Controlling Effects Against Serpentine Leafminer (Liriomyzatrifolii)

A kidney bean leaf segment having eggs of serpentine leafminer uniformlylaid thereon, was dipped for about 10 seconds in an insecticidalsolution prepared to bring the concentration of the compound of thepresent invention to 25 ppm or 12.5 ppm, and then dried in air. A wetfilter paper was laid in a plastic cup having a diameter of 9 cm and aheight of 4 cm, and the dried kidney bean leaf segment was placedthereon. Then, after putting a cover thereon, it was left in a constanttemperature chamber at 25° C. with lightening. The number of old instarlarvae and the number of pupae were counted for 6 to 8 days after thetreatment, and the protective value was calculated by the followingequation. The protective value was obtained at 25 ppm with respect tothe above-mentioned compound Nos. 9, 14 and 23, whereby all compoundsshowed high controlling effects with a protective value of at least 90%,and the protective value at 12.5 ppm was obtained with respect to theabove-mentioned compound Nos. 2, 3, 11, 12, 15 to 18, 20 and 22, wherebyall compounds showed high controlling effects with a protective value ofat least 90%.Protective value (%)=(1−((number of old instar larvae+the number ofpupae at treated section)/(number of old instar larvae+number of pupaeat untreated section)))×100

Test Example 6

Test on Controlling Effects Against Thrips palmi

From a cucumber planted in a pot, all leaves except for first true leafwere cut off. The remaining leaf was dipped for about 10 seconds in aninsecticidal solution prepared to bring the concentration of thecompound of the present invention to 50 ppm and dried in air. Then, acucumber leaf segment infested with first instar larvae was placed onthe above treated leaf. Next day, the cucumber leaf segment was removed,and the number of larvae moved to the treated leaf was counted. A wetfilter paper was laid in a plastic cup having a diameter of 9 cm and aheight of 4 cm, and the treated leaf cut off was placed thereon. Then,after putting a cover thereon, it was left in a constant temperaturechamber at 25° C. with lightening. The number of survived insects wascounted for 12 to 15 days after the treatment, and the protective valuewas obtained in the same manner as in the above Test Example 2. Theprotective value was obtained with respect to the above-mentionedcompound Nos. 11, 12, 16, 22, 38 and 39, whereby all compounds showedhigh controlling effects with a protective value of at least 90%.

Test Example 7

Test on Controlling Effects Against Twenty-eight-Spotted Ladybird(Epilachna vigintioctopunctata)

An eggplant leaf segment was dipped for about 10 seconds in aninsecticidal solution prepared to bring the concentration of thecompound of the present invention to 25 ppm or 12.5 ppm and dried inair. A wet filter paper was laid in a plastic cup having a diameter of 9cm and a height of 4 cm, and the dried eggplant leaf segment was placedthereon. Five first-second instar larvae of twenty-eight-spottedladybird were released thereon and after putting a cover thereon, leftin a constant temperature chamber at 25° C. with lightening. Deadinsects were counted for 4 to 6 days after the release, and themortality was obtained in the same manner as in the above TestExample 1. Here, moribund insects were counted as dead insects. Themortality was obtained at 25 ppm with respect to the above-mentionedcompound Nos. 9 and 11, whereby all compounds showed high controllingeffects with a mortality of at least 90%, and the mortality was obtainedat 12.5 ppm with respect to the above-mentioned compound Nos. 3, 16, 22,38 and 39, whereby all compounds showed high controlling effects with amortality of at least 90%.

Test Example 8

Test on Controlling Effects Against Housefly (Musca domestica)

10 g of a culture medium was put into a plastic cup having a diameter of6 cm and a height of 3 cm, and then, 10 ml of an insecticidal solutionprepared to bring the concentration of the compound of the presentinvention to 200 ppm, was added and mixed. 20 or 30 larvae at 4-day oldwere released, and after putting a cover thereon, it was left in aconstant temperature chamber at 25° C. with lightening for from 15 to 16days. Thereafter, the number of adults was counted, and the percentinhibition of emergence was obtained by the following equation. Thepercent inhibition of emergence was obtained with respect to theabove-mentioned compound Nos. 3, 9, 11, 12 and 14 to 20, whereby allcompounds showed high controlling effects with a percent inhibition ofemergent of at least 90%.Percent inhibition of emergence (%)=(1−(number of adults/number ofreleased larvae))×100

Test Example 9

Test on Controlling Effects Against Formosan Subterranean Termite(Coptotermes formosanus)

A filter paper was laid in a glass petri dish having a diameter of 9 cm,and 1 ml of an insecticidal solution prepared to bring the concentrationof the compound of the present invention to 500 ppm was applied. Then,10 workers and one soldier of Formosan subterranean termite werereleased, and after putting a cover, left in a constant temperaturechamber at 25° C. with lightening. The number of dead workers wascounted 6 days after the treatment, and the mortality was obtained bythe following equation. The mortality was obtained with respect to theabove compound Nos. 3, 9, 11, 12, 14 to 16 and 22, whereby all compoundsshowed high controlling effects with a mortality of at least 90%.Mortality (%)=(number of dead workers/10)×100

Test Example 10

Test of Systemic Effects Against Common Cutworm (Spodoptera litura)

10 ml of an insecticidal solution prepared to bring the concentration ofthe compound of the present invention to 800 ppm or 200 ppm, was appliedto the foot of cabbage at the 5th to 6th leaf stage planted in a pot. Awet filter paper was laid in a petri dish having a diameter of 9 cm, anda cabbage leaf segment cut out at ten days after the treatment wasplaced thereon. Ten second-third instar larvae of common cutworm werereleased thereon, and after putting a cover, left in a constanttemperature chamber at 25° C. with lightening. Dead larvae were countedfor 4 to 5 days after the release, and the mortality was obtained in thesame manner as in the above Test Example 1. Here, moribund insects werecounted as dead insects. The mortality at 800 ppm was obtained withrespect to the above-mentioned compound No. 8 whereby it showed highcontrolling effects with a mortality of at least 90%, and the mortalityat 200 ppm was obtained with respect to the above compound Nos. 3, 9,11, 16, 18 and 22, whereby all compounds showed high controlling effectswith a mortality of at least 90%.

Test Example 11

Test on Controlling Effects Against Haemaphysalis longicornis

On an inner surface of a petri dish having diameter of 9 cm, 1 ml of anacetone solution of a sample compound (concentration: 10 μg/ml) wasdropwise applied by a micropipette. On the other hand, as a controlsection, 1 ml of acetone was dropwise applied in the same manner. Theinner surface of the petri dish was dried, and then about 100 larvalticks were put, and the petri dish was covered with a polyethylene sheetand sealed with an elastic band. Thereafter, except for the observationtime, the petri dish was left to stand at a constant temperature of 25°C. under a relative humidity of 100% and under a constantly darkcondition. The observation was carried out every time after putting thelarval ticks in the petri dish (after 5 minutes, 10 minutes, 15 minutes,20 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 4 hours, 6 hoursand 24 hours). The number of knockdown ticks after the contact with theinsecticidal compound was recorded. The foregoing operation was repeatedtwice.

The knockdown rate at each observation time was corrected by thefollowing abbott correction formula. Then, a probit-time linear line wasdrawn, and the median knockdown time (KT₅₀ value) was obtained. Withrespect to the KT₅₀ values of the respective sample compounds, they were9 minutes and 8 minutes with the above-mentioned compound No. 3, and 7.5minutes and 6 minutes with the above-mentioned compound No. 9, whilethey were 80 minutes and 40 minutes with the following comparativecompound A and 120 minutes and 80 minutes with the following comparativecompound B.Corrected knockdown rate (%)=[(non-knockdown rate in controlsection−non-knockdown rate in treated section)/non-knockdown rate incontrol section]×100

Comparative compound A is the following compound which is compound 484in WO03/24222, compound 497 in WO03/15518 and compound 2 in WO03/15519.

Comparative compound B is the following compound which is compound 509in WO03/24222, compound 530 in WO03/15518 and compound 27 in WO03/15519.

Test Example 12

Test on Controlling Effects Against Cat Flea (Ctenocephalides felis)

0.5 ml of an acetone solution of the compound of the present inventionprepared to be 5.3 ppm was dropped in a glass tube having a flat bottom(inner diameter: 2.6 cm, bottom area: 5.3 cm², height 12 cm). Theacetone was evaporated at room temperature to have a dry film containingthe compound of the present invention formed on the bottom surface. Tenadults of cat flea (not-yet-blood-sucked adults within five days afteradult emergence) were put therein and exposed to the compound of thepresent invention. The test was carried out continuously three times.

Dead cat flea were counted 48 hours after the exposure and the mortalitywas obtained in the same manner as in the above Test Example 1. Themortality was obtained with respect to the above-mentioned compound No.16, whereby it showed high controlling effects with a mortality of atleast 90%.

Formulation Example 1

(1) Compound of the present invention 20 parts by weight (2) Clay 72parts by weight (3) Sodium lignin sulfonate 8 parts by weight

The above components are uniformly mixed to obtain a wettable powder.

Formulation Example 2

(1) Compound of the present invention 5 parts by weight (2) Talc 95parts by weight

The above components are uniformly mixed to obtain a dust.

Formulation Example 3

(1) Compound of the present invention 20 parts by weight (2)N,N′-dimethylacetamide 20 parts by weight (3) Polyoxyethylenealkylphenylether 10 parts by weight (4) Xylene 50 parts by weight

The above components are uniformly mixed and dissolved to obtain anemulsifiable concentrate.

Formulation Example 4

(1) Clay 68 parts by weight (2) Sodium lignin sulfonate 2 parts byweight (3) Polyoxyethylenealkylaryl sulfate 5 parts by weight (4) Finesilica powder 25 parts by weight

A mixture of the above components is mixed with compound of the presentinvention in a weight ratio of 4:1 to obtain a wettable powder.

Formulation Example 5

(1) Compound of the present invention 50 parts by weight (2) Oxylatedpolyalkylphenyl 2 parts by weight phosphate-triethanolamine (3) Silicone0.2 part by weight (4) Water 47.8 parts by weight

The above components are uniformly mixed and pulverized to obtain a baseliquid, and

(5) Sodium polycarboxylate 5 parts by weight

(6) Anhydrous sodium sulfate 42.8 parts by weight are added, and themixture is uniformly mixed, granulated and dried to obtainwater-dispersible granules.

Formulation Example 6

(1) Compound of the present invention 5 parts by weight (2)Polyoxyethyleneoctylphenyl ether 1 part by weight (3) polyoxyethylenephosphoric 0.1 part by weight acid ester (4) Granular calcium carbonate93.9 parts by weight

The above components (1) to (3) are preliminarily uniformly mixed anddiluted with a proper amount of acetone, and then the mixture is sprayedonto the component (4), and acetone is removed to obtain granules.

Formulation Example 7

(1) Compound of the present invention 2.5 parts by weight (2)N-methyl-2-pyrrolidone 2.5 parts by weight (3) Soybean oil 95.0 parts byweight

The above components are uniformly mixed and dissolved to obtain anultra low volume formulation.

Formulation Example 8

(1) Compound of the present invention 40 parts by weight (2) Oxylatedpolyalkylphenylphosphate- 2 parts by weight triethanolamine (3) Silicone0.2 part by weight (4) Zanthan gum 0.1 part by weight (5) Ethyleneglycol 5 parts by weight (6) Water 52.7 parts by weight

The above components are uniformly mixed and pulverized to obtain awater-based suspension concentrate.

Formulation Example 9

(1) Compound of the present invention 10 parts by weight (2) Diethyleneglycol monoethyl 90 parts by weight ether

The above components are uniformly mixed to obtain a solubleconcentrate.

The entire disclosures of Japanese Patent Application No. 2004-041295filed on Feb. 18, 2004, Japanese Patent Application No. 2004-133722filed on Apr. 28, 2004, Japanese Patent Application No. 2004-261507filed on Sep. 8, 2004 and Japanese Patent Application No. 2004-295778filed on Oct. 8, 2004 including specifications, claims and summaries areincorporated herein by reference in their entireties.

1.N-[6-[[(cyclopropylmethyl)amino]carbonyl]-2-methylphenyl]-1-(3-chloro-2-pyridyl)-3-(trifluoromethyl)-1H-pyrazole-5-carboxamide.2.N-[4-chloro-2-methyl-6-[[α-methyl-(cyclopropylmethyl)amino]carbonyl]-phenyl]-3-(trifluoromethyl)-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide.3.N-[4-chloro-2-methyl-6-[[α-methyl-(cyclopropylmethyl)amino]carbonyl]-phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide.4.N-[2-bromo-4-chloro-6-[[α-methyl-(cyclopropylmethyl)amino]carbonyl]-phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide.